Alexandria Engineering Journal (2022) 61, 5213–5222

H O S T E D BY
Alexandria University

Alexandria Engineering Journal

www.elsevier.com/locate/aej
www.sciencedirect.com

Biosorption of dye by immobilized yeast cells on the

surface of magnetic nanoparticles
Rana Abbas Azeez *, Firas Khaleel Ismael Al-Zuhairi

Petroleum Technology Department, University of Technology, Baghdad, Iraq

Received 3 July 2021; revised 7 October 2021; accepted 19 October 2021

Available online 31 October 2021

KEYWORDS Abstract Bioremediation has been considered as an efficient environmental pollution control tech-
Fe3O4 magnetic nanoparti- nique. It relies on microbial cells like yeasts which are unicellular organisms that are widely used
cles; due to their availability, easily cultured, economical, and eco-friendly. The immobilization of living
Biosorption; cells on the magnetic nanoparticles surface is a novel technique to obtain nanobiocatalyst. In this
Immobilization technique; work, yeast cells of Saccharomyces cerevisiae were immobilized on the surface of Fe3O4 magnetic
Methyl orange; nanoparticles (MNPs) as a biosorbent to remove methyl orange (M.O) dye from aqueous solution
Saccharomyces Cerevisiae in a batch system through biosorption mechanism. MNPs were characterized using XRD and SEM.
FTIR was used to characterize the biosorbent before and after biosorption. The experiments were
carried out using various factors such as contact time, pH, M.O concentration, biosorbent dosage,
and temperature. The results indicated that significant removal efficiency of 96.52 % was obtained
at the optimum conditions of pH 6.5, 50 mg/l M.O initial concentration, 1.5 g/l biosorbent dosage,
110 rpm shaker, and 35 °C temperature. Adsorption isotherm studies illustrated that the data of
biosorption of M.O dye from aqueous solution followed the Freundlich model with a correlation
coefficient of R2 > 0.99. The values of biosorption thermodynamic parameters were estimated
and the results showed that the biosorption mechanism of M.O dye was exothermic due to the neg-
ative value of DHo (-7.8737 KJ/mol), and spontaneous due to the negative values of DGo (
5108.22,

6286.16,
7475.21) at various temperatures. Moreover, the positive value of DSo (28.47 J/mol)
pointed out to an increment in randomness at the interface of the aqueous solution-biosorbent.
Ó 2021 THE AUTHORS. Published by Elsevier BV on behalf of Faculty of Engineering, Alexandria
University. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/
licenses/by-nc-nd/4.0/).

1. Introduction

The increment in population expansion around the world and

the rapid development of technology has caused environmen-
* Corresponding author. tal disturbance and increased pollution, as polluted water is
E-mail addresses: Rana.A.Azeez@uotechnology.edu.iq (R.A. Azeez),
the most common type of environmental pollution [1]. Dyes
150009@uotechnology.edu.iq (F.K.I. Al-Zuhairi). are considered as pollutants generated from textile, paper, rub-
Peer review under responsibility of Faculty of Engineering, Alexandria ber, leather, plastic, and printing industries. Due to losses
University. some quantities of dyes through the painting process, dyes
https://doi.org/10.1016/j.aej.2021.10.044
1110-0168 Ó 2021 THE AUTHORS. Published by Elsevier BV on behalf of Faculty of Engineering, Alexandria University.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
5214
are classified according to many factors such as charge of the
molecule, cationic nature (e.g. methylene blue), and anionic
nature (e.g. methyl orange). These types have wide applica-
tions in printing and research laboratories [2].
The negative effects of dyes on the environment such as
toxicity, death of aquatic organisms, and human diseases lead
to genetic mutations [3]. Therefore, many techniques have been
established to eliminate dyes from industrial effluents such as
coagulation/flocculation, adsorption, membrane treatment,
bioremediation, photochemistry and oxidation [4–6]. Bioreme-
diation is a biotechnique involving the use of living organisms
to eliminate pollutants from water, air, and soil through sev-
eral mechanisms such as biosorption, bioaccumulation, and
biodegradation [1]. Bioaccumulation is the gradual accumula-
tion of contaminants into the living tissue of an organism [7].
Biodegradation is the breakdown of organic matter by living
cells of microorganisms [8]. Biosorption is a cost-efficient
and eco-friendly mechanism of removing the contaminants
from wastewater, particularly those that cannot easily
biodegradable like dyes. Dead or living organisms like bacte-
ria, fungi, algae, and yeasts as well as agro waste are consid-
ered as an excellent biosorbent capable for removing
pollutants from wastewater [1,9–11]. The advantages of
biosorption among other mechanisms utilized to eliminate pol-
lutants from aqueous solutions are low cost of biosorbent,
rapid process, high uptake of contaminants due to high bind-
ing sites under various conditions of pH and temperature,
renewal of the bioabsorbent for reuse as well as ease of storage
[12]. Yeasts are one of the microbial cells used as an excellent
biobsorbent for removing organic contaminants from efflu-
ents. They are single-celled organisms classified as fungi, and
they play a significant part in the bioremediation of contami-
nated water due to they are inexpensive and very valuable.
Yeast technology was developed by gene engineering and
immobilized cells, and is applied to augment the biodegrada-
tion process by converting organic matter into non-toxic mate-
rials [13].
Several effective techniques have been used to modify
microbial cells, such as pretreatment and immobilization,
where immobilizing of living cells is a major part of the bios-
timulation process [14]. Moreover, it has the ability to restrict
cell motility, which leads to an increase in the potential for bio-
absorption of various bio-sorbents as compared to suspended
cells [15–17]. Therefore, microbial cell immobilization technol-
ogy has proven to be efficient and promising in controlling
environmental pollution by more than 60% [18].
Nanotechnology is an emerging technology and is widely
used in multi-disciplinary fields. It has acquired more attention
as it offers single physico-chemical and morphological charac-
teristics. Nanomaterials have been applied in environmental
remediation due to their ultra-small size and shape. Magnetic
iron nanoparticles have great potential in environmental treat-
ment due to they have antimicrobial properties. They can be
applied in decolorization of effluents using adsorption tech-
nique [19].
The immobilization of microbial cells with magnetic
nanoparticles is a novel technique, as magnetic nanoparticles
are able to adhere to the biomass surface through interactions
like hydrophobic, electrostatic, and van der Waals forces [20].
The advantages of magnetic nanoparticles when compared to
R.A. Azeez, F.K.I. Al-Zuhairi
suspended organisms and the traditional techniques of cells
immobilization are the recovery of catalysts from the liquid
phase, along with the great sorption performance due to their
high surface area [21].
Several studies were conducted to decolorize from aqueous
solutions using various biocatalysts. Upendar, G. et al. (2016)
[22] applied biological treatment to remove methylene blue
from simulated solution using immobilized Bacillus subtilis
with calcium alginate in the batch and continuous systems.
Suganya, K. and Revathi, K. (2016) [23] showed that high
removal efficiency of reactive dyes from textile effluents was
recognized by immobilization of P.putida and B.licheniformis.
Siddeeg, S.M. et al. (2020) [24] obtained 98% and 96%
removal efficiency of RO16 and MB dyes, respectively, by
immobilization of manganese peroxidase enzyme on the sur-
face of magnetic nanocomposite (Fe3O4/chitosan). Diorio, L.
A. et al. (2021) [25] observed that high removal of two types
of dyes was achieved by applying immobilization technique
using filamentous fungi in the spherical cartridges of the biore-
actor. Estrada, A. K. C. et al. (2021) [26] reported that the
removal rate of M.O dye from synthesized solution of more
than 90 % was obtained using magnetic-activated carbon as
adsorbent at 30 mg/l M.O concentration, 135 min contact
time, 20 °C temperature and 0.02 g adsorbent dosage. Alsaiari,
N.S. et al. (2021) [27] showed that the adsorption capacity to
remove M.O from the aqueous solution was about 95 mg/g
at 100 ppm initial concentration using a magnetic polymer
nanocomposite as an adsorbent under conditions of 40 min
of contact time, 25 °C temperature and 100 mg sorbent dosage.
Microbial cell immobilization is a novel technique and a
valuable strategy in bioremediation; moreover, magnetic
nanoparticles have attracted researchers interest in stabilizing
microbial cells. Therefore, this work highlights the efficiency
of immobilization yeast cells of Saccharomyces cerevisiae on
the surface of Fe3O4 magnetic nanoparticles (MNPs) as a
biosorbent to remove methyl orange dye from aqueous solu-
tion in a batch system. The influence of various factors such
as contact time, pH, biosorbent dosage, M.O concentration,
and temperature on the biosorption efficiency was examined
at experimental tests.
2. Materials and methods
2.1. Materials
2.1.1. Chemicals
All materials used in the experiments including ferric chloride
(FeCl36H2O), glucose (C6H12O6), ferrous sulfate heptahy-
drate (FeSO47H2O), yeast extract, ammonium hydroxide
(NH4OH), peptone, potassium dihydrogen phosphate (KH2
PO4), magnesium sulfate heptahydrate (MgSO47H2O), zinc
sulfate (ZnSO4), ammonium sulfate ((NH4)2SO4), sodium
chloride (NaCl), sodium hydroxide (NaOH) and hydrochloric
acid (HCl) were bought from Sigma–Aldrich, USA.
2.1.2. Microorganisms
The microorganism used in this study, Saccharomyces Cere-
visiae, was purchased from the local market and is of Turkish
origin.
Biosorption of dye by immobilized yeast cells on the surface of magnetic nanoparticles 5215

2.2. Fe3O4 MNPs preparation unit weight of immobilized yeast cells at a given time (t) was
estimated using Eq. (1) [11].
MNPs were prepared using co-precipitation method according ðCi
CtÞV
to the following steps. First, 10 ml of 0.25 M FeSO47H2O was qðtÞ ¼ ð1Þ
m
mixed with 20 ml of 0.25 M FeCl36H2O followed by drop-wise
of 30 ml from 12 M NH4OH to the mixture with continued Where Ci and Ct (ppm) are the concentrations of initial M.O
mixing for one hour. Second, an exterior magnet was utilized and at any time, respectively; V is the M.O volume in the aque-
to separate the precipitate from the NH4OH solution and ous solution; and m is the immobilized yeast weight. The
washed many times with deionized water to purify it from immobilized yeast efficiency for biosorption of M.O from
NH4OH. Finally, the wet precipitate was dried overnight at aqueous solution was estimated using Eq. (2) [11]:
105 C and then ground to a fine powder by utilizing a mortar
ðCi
CtÞ
and pestle [28]. Removal efficiency ¼  100 ð2Þ
Ci
2.3. Microorganisms cultivation
3. Results and discussion
Saccharomyces Cerevisiae was enriched in the medium of a
group of nutrients dissolved in one liter of distilled water which 3.1. Characterization of Fe3O4 MNPs
included 50.0 g glucose, 30.0 g peptone, 10.0 g yeast extract,
1.0 g KH2 PO4, 1.0 g (NH4)2SO4, 0.5 g MgSO47H2O, 0.5 g
NaCl and 0.01 g ZnSO4. The organisms were incubated in sha- 3.1.1. X-ray diffraction (XRD)
ker at 110 rpm and 28 °C. Post-growth yeast cells were har-
Fig. 1 shows the XRD pattern of MNPs reflecting the peak
vested after 24 h via centrifugation at 2500 rpm for 40 min,
intensity against the 2h angle position and obtained using X-
washed with distilled water and re-centrifuged twice. Then,
ray test with 0.154060 nm Cu ka radiation, 40.0 kV, and
the active cells were dried for 24 h [29].
30.0 mA. It is clear that the intensity peaks corresponded to
F3O4 magnetite at diffraction planes of (2 2 0), (3 1 1), (4 0 0),
2.4. Immobilized yeast cells with Fe3O4 MNPs
(4 2 2) (5 1 1) and (4 4 0). These diffraction planes are obtained
at 2h angle positions of 30.26°, 35.6313°, 43.27°, 53.64°,
The MNPs of Fe3O4 were dissolved in the temporary phos- 57.18° and 62.77°, respectively. The same result was obtained
phate solution with pH 7 and stored at 25 °C for 12 h. Cul- by Loh K-S et al. (2008) [30]. The crystalline size of prepared
tured S. cerevisiae was diluted with sterile physiological Fe3O4 MNPs was estimated utilizing Scherrer equation as
solution (0.9% NaCl) and added to the mixing, then sharked illustrated in Eq. (3) [31].
with Fe3O4 MNPs for 24 h. The yeast cells supported on the
surface of Fe3O4 MNPs were separated utilizing a permanent kk
Dc ¼ ð3Þ
magnet, after which, they were washed with distilled water b1=2cosh
and physiological solution several times. Thus, yeast cells
Where Dc is the crystalline diameter in nm, k is the Scherrer
loaded with MNPs are ready for the biosorption of M.O from
constant (0.89), k is the wavelength of X-ray radiation
aqueous solution [29].
(0.15060 nm), bø is (FWHM) of the diffraction peak
(0.00822 rad), and h is the peak diffraction angle (17.81565°).
2.5. Batch biosorption studies
The estimated average crystalline diameter of the Fe3O4 MNPs
was approximately 16.3 nm.
Biosorption experiments of methyl orange as model pollutant,
an anion dye with a molecular formula (C14H14N3NaO3S),
were performed using a batch system realized using immobi-
lized yeast cells on the surface of Fe2O3 MNPs as a biosorbent
in aqueous solution. Biosorbent of 0.1 g was added into 100 ml
of M.O in a 250 ml conical flask, and agitated in rotary shaker
at 110 rpm for various time periods (5, 10, 15, 20, 30, 60, 90,
120 and 250 min) at temperature of 25 °C. The pH of a solu-
tion was adjusted to the desirable value utilizing (1 N HCl and
1 N NaOH) [27]. All media were autoclaved at 121 °C for
30 min prior being utilized in the experiments. The influence
of acidity with the pH values of 2–10 on the biosorption pro-
cess and the impact of initial concentration of M.O (50, 100
and 150 mg/l) at a specified time was studied in this work.
The influence of different temperatures (25, 30 and 35 °C)
and various dosages of biosorbent on the biosorption was also
investigated. The concentration of M.O solution was estimated
by utilizing a UV-Spectrophotometer at wavelength of 540 nm.
Each experiment was repeated three times and the mean value
was taken. The biosorption q(t) (mg/g) of M.O amount per Fig. 1 The XRD pattern of Fe3O4 MNPs.
5216
3.1.2. FTIR**a
Fourier Transform Infrared Spectroscopy (FTIR) is an effi-
cient characterization technique utilized in this work to iden-
tify the functional groups and distinguish covalent bonding
for biosorbent (immobilized yeast cells on the MNPs) before
and after biosorption of dye from aqueous solution as shown
in Figs. 2 and 3. The absorption spectrum of biosorbent was
recorded in the wave range of 422.41–4000 cm
1. The broad-
band between 3901.99 and 3739.97 cm
1 is typically ascribed
to the signal bond of O-H stretching and adsorbed water mole-
cules. The characteristic biosorption peak at 3275.13 cm
1 is
assigned to stretching of –CH2– bond, while the peak at
2868.15 cm
1 is assigned to –CH– bond [32]. The characteristic
peak at 1651.07 cm
1 is mostly ascribed to some of the oxygen
functional groups like carbonyl and carboxylic groups [33].
The peak at 588.2 cm
1 is referred to the Fe–O group of nano
Fe3O4 [34]. From relevant results of diagnosis FTIR for
biosorbent, the observed differences in the absorbance peaks
after M.O dye biosorption were attributed to the interaction
between M.O dye and different functional groups. Therefore,
we can conclude that the functional groups play a significant
part in the biosorption.
3.1.3. SEM**a
SEM images of Fe3O4 MNPs and yeast cells immobilized on
the surface of MNPs are shown in Fig. 4. It is obvious that
semispherical and irregular particles in the clustered form are
recognized. The sizes of these particles are in the range of
138.2–219.1 nm and 87.46–231.4 nm for MNPs and yeast cells
immobilized on the surface of MNPs, respectively. The
decrease in particle size was identified after the immobilization
of yeast cells on the surface of MNPs which attributed to the
contribution of immobilization technique in reducing the par-
ticle size of MNPs. Reducing the particle size of Fe3O4 MNPs
increased the surface area which enhanced the biosorption
mechanism. An analogous result was noticed by Mahmoud
et al. (2015) [35], where the immobilization of yeast on the sur-
face of activated carbon and nano-Fe3O4 as a sorbent reduced
the particle size.
Fig. 2 FTIR of biosorbent before biosorption.
R.A. Azeez, F.K.I. Al-Zuhairi
3.2. Optimization of biosorption
Yeast cells immobilized on the surface of Fe3O4 MNPs were
prepared as a biosorbent to verify their ability to remove M.
O dye (85% purity, Sigma-Aldrich) from aqueous solution.
The experiments were conducted under the influence of several
factors such as initial concentration of M.O dye, contact time,
initial pH, biosorbent dosage, and temperature to approach
the optimum conditions for the biosorption process.
3.2.1. Effects of contact time and initial M.O concentration
Equilibrium time theory has been established as one of the
most important variables for designing economic systems for
wastewater treatment. Therefore, from an economic point of
view, the contact time for the biosorption of M.O dye from
aqueous solution should be adjusted. Different initial concen-
trations of M.O were used (150, 100 and 50 mg/l) in a batch
adsorption mode. The pH value in these experiments was set
at 6.5 with 0.5 g/l of biosorbent under continuous shaking
and at 25 °C. Figs. 5 and 6 showed that the M.O concentration
started to decrease and the removal percentage tended to a
high value with an increment in the contact time as the equilib-
rium was achieved at approximately 140 min. However, M.O
removal was increased with a diminish in the initial M.O con-
centration as removal efficiencies of 69.6, 73.5 and 83% were
obtained at the initial concentration of 150, 100, and 50 mg /
l, respectively, after the equilibrium time was reached to
approximately 140 min for all tests due to the increased inter-
action between the dye molecules and the binding sites that
exist in the adsorbed surface. Therefore, the increased initial
concentration reduced the biosorption efficiency due to satura-
tion of the biosorption sites [27,36].
3.2.2. Effect of biosorbent dosage
A biosorbent dosage is an active factor that affects the removal
of M.O dye in aqueous solution. In this study, the influence of
biosorbent dosage concentration on M.O dye removal was
studied using (0.5, 1.0, and 1.5) g/l of biosorbent impregnated
in 250 ml of an aqueous solution contaminated with (50 mg/l)
Biosorption of dye by immobilized yeast cells on the surface of magnetic nanoparticles 5217

Fig. 3 FTIR of biosorbent after biosorption.

Fig. 4 (a) SEM images of Fe3O4 MNPs, (b) Yeast cells immobilized on the surface of Fe3O4 MNPs.

Fig. 5 Influence of time on the concentration of M.O at pH 6.5, Fig. 6 Influence of time on the removal (%) at pH 6.5, 110 rpm
110 rpm and 25 °C. and 25 °C.
5218 R.A. Azeez, F.K.I. Al-Zuhairi

of M.O dye at pH 6.5 and 25 °C. Analysis of the results

showed that the concentration of M.O dye decreases with
increasing dosage of the biosorbent (Figs. 7 and 8). The opti-
mal removal efficiency of 92% was obtained at the 1.5 g/l
biosorbent dosage after 140 min. Moreover, 87.82% and
83.04% removal efficiencies were obtained at 1 g/l and 0.5 g/
l biosorbent dosage, respectively. The increase in the removal
efficiency of M.O dye with increasing dosage concentration
was attributed to an increment in the adsorption sites [31].

3.2.3. Effect of initial pH

The pH value is another considerable factor that has an impor-
tant influence on the biosorption efficiency of dyes due to its
impact on the surface charges of sorbent and dye molecules.
Accordingly, the influence of pH in the range of 2–10 on decol-
orization of M.O dye was studied with other constant param-
eters such as 1.5 g /l dosage of biosorbent, 50 mg/l M.O dye
concentration, 25 °C temperature and 140 min contact time. Fig. 8 Influence of time on the removal % at pH 6.5, 50 mg/l M.
The results evinced that increasing the pH led to a decline in O concentration and 25 °C.
the concentration of the M.O dye and an increment in the
removal efficiency (Fig. 9). It is evident that at the initial
pH, the removal efficiency was about 85% and improved to
89.56% and 92.17% at pH 4 and 6, respectively. A progressive
decrease in the removal efficiency was observed with a further
increment in the pH value from 8 to 10. Therefore, the best
removal efficiency was obtained at pH 6.5.
The enhancement in the removal efficiency of the M.O dye
from aqueous solution was recognized when the pH was
increased from 2 to 6 due to the ionization of Fe3O4 MNPs
surface which led to the appropriate biosorption of the M.O
dye. On the other hand, the removal efficiency decreased at
the highest pH level due to the gradual precipitation of the
hydroxide [26].

3.2.4. Effect of temperature

Temperature is a considerable factor in removing M.O dye
from aqueous solution. The effect of different temperatures
ranged from 25 to 35 °C in a batch system at optimum condi-
tions of 1.5 g/l dosage of biosorbent, pH 6.5 and 50 mg/l M.O
dye concentration was studied. The relationship between tem- Fig. 9 Influence of pH on the removal % at 1.5 g/l biosorbent,
perature and removal percentage is shown in Fig. 10. The pH 6.5, 50 mg/l M.O concentration and 25 C.

Fig. 7 Influence of time on the dye concentration at pH 6.5, Fig. 10 Influence of temperature on the removal % at 1.5 g/l
50 mg/l M.O concentration and 25 °C. biosorbent, pH 6.5 and 50 mg/l M.O concentration.
Biosorption of dye by immobilized yeast cells on the surface of magnetic nanoparticles 5219

results revealed that at 25 °C, the removal efficiency was

94.6 %, Rajhans, G. et al. 2020 [39]

62.1%, Ülküye Dudu Gül 2013 [37]
92.17% and with rising temperature from 30 to 35 °C, the

53.62%, Takey, M. et al., 2014[38]

removal efficiency enhanced to 94.78% and 96.52%, respec-
tively. It was evident that the M.O removal efficiency aug-

96.52 %, In present study

mented gradually with the temperature rise from 25 °C to

Removal efficiency (%)

35 °C, which increased the rate of dye biosorption and acceler-
ated the transfer of dye ions from the liquid phase to the sur-
face of the biosorbent.
It is evident that effective bioremoval of dyes from textile
effluent depends on the selected appropriate mechanism.
Immobilization is considered as a biotechnique tool that
greatly enhances the potential of bioprocessing [11,15]. In the
present study, immobilization of yeast cells (Saccharomyces
Cerevisiae) on the surface of Fe3O4 MNPs was applied to
5.5, 1 mg/l, ambient temperature, 40 min

improve the biosorption efficiency as methyl orange dye was

removed from the aqueous solution. The results evinced that
the best removal efficiency of 96.52 % was acquired at the
optimum conditions of pH 6.5, 50 mg/l M.O dye concentra-
6.5, 50 mg/l, 35 °C, 140 min

tion, 1.5 g/l immobilized yeast cells dosage, 110 rpm shaker,
and 35 °C temperature. Comparing the results obtained with
3, 100 mg/l, 30 °C, 48 h

6, 0.5 g/l, 35 °C, 48 h

previous works in which other types of fungal strains were

used such as bio-base material in the bioremoval of dyes can
Optimum conditions

be illustrated in Table 1. We recognized that the highest

removal of M.O dye from the aqueous solution was due to
the immobilization of the yeast biomass on the magnetic nano
Mechanisms utilized to remove dyes with different bio-base material (Values from previous studies).

surface results in increased surface area that boosts

biosorption.
pH
pH
pH
pH

3.3. Adsorption isotherm study

Biosorption of M.O, immobilized cells with (Fe3O4 MNPs)

In the present study, the equilibrium data for biosorption of

M.O dye from aqueous solution was modeled with two
adsorption isotherms models (Freundlich and Langmuir).
The Freundlich isotherm can be utilized for the description
of the heterogeneous surface (multilayer adsorption) with the
interaction among adsorbed molecules, while Langmuir iso-
therm proposed to describe monolayer adsorption occurred
Biosorption of anion dye (live cells)

at all sites of the homogenous surface. The linear forms of Fre-

Biosorption of M.O (dead cells)

undlich and Langmuir’s models were expressed mathemati-

cally by Eqs. (4) and (5), respectively [40,41]. The
dimensionless separation factor (RL) was estimated using Eq.
Biodegradation of M.O

(6) which is a significant factor in controlling whether the

adsorption is favorable or not [42].
Mechanisms

Geotrichum candidum (Fungal strain)

Saccharomyces Cerevisiae (Yeast)
Rhizopus arrhizus (Fungal strain)
Aspergillus flavus (Fungal strain)
Bio-base material
Table 1

Fig. 11 Freundlich adsorption isotherms.

5220 R.A. Azeez, F.K.I. Al-Zuhairi

Fig. 12 Langmuir adsorption isotherms.

Fig. 13 Adsorption thermodynamic.

Table 2 Freundlich and Langmuir parameters.

Table 3 Estimated values of thermodynamic parameters.
Freundlich Langmuir
T (K) DGo (J/mol) DHo (KJ/mol) DSo (J/mol)
n k (mg/g) R2 qo b R2 RL
(mg/L) (mg/g) (L/mg) 298.15
5108.22
7.8737 28.47
303.15
6286.16
1.85 25.89 0.9958 277.1482 0.050 0.9861 0.1177
308.15
7475.21

1 parameters such as change in free energy (DGo ), change in

log qe ¼ log k þ log Ce
n
1 1 1 q
¼ þ
qe bqo Ce qo
1 DGo ¼
RT lnKC
RL ¼
ð1 þ bCi Þ
Where qe (mg/g) is the sorption capacity at equilibrium time, k
and n are Freundlich constants refer to capacity and intensity
of adsorption, respectively, determined via plotting log qe
against log Ce (Fig. 11), Ce and Ci (mg/l) are equilibrium and
initial concentrations, respectively, b (l/mg) and qo (mg/g) are
adsorption coefficient and monolayer saturation capacity,
respectively, for Langmuir isotherm computed from the slope
and intercept of the linear plot of q1e against C1e as shown in
Fig. 12.
As shown in Table 2 and Figs. 11, 12, the value of R2 is
greater for Freundlich isotherm that indicates it is best fitted
to the adsorption data, which detects that the adsorption pro-
cess was superior with the heterogeneous surface. Further-
more, the n value for Freundlich isotherm is more than unity
which corresponds to a favorable adsorption system [42].
Table 2 also showed that the maximum monolayer satura-
tion capacity for Langmuir isotherm was found to be 277.1482
(mg/g), and the biosorption coefficient was 0.050 (l/mg). The
value of RL was about 0.1177 calculated at the initial concen-
tration of M.O dye (150 mg/l) which is considered favorable
adsorption since it locates in the range ð0 < RL < 1Þ [42].
3.4. Thermodynamic study
In the present study, to determine whether the process is spon-
taneous or unspontaneous, the value of thermodynamic
ð4Þ enthalpy (DHo ), and change in entropy (DSo ) were evaluated
using the following Eqs. (7)–(9) [43].
ð5Þ KC ¼ e ð7Þ
Ce
ð8Þ
ð6Þ
 o  o
DS DH
lnKC ¼
ð9Þ
R RT
Where KC represents equilibrium constant of the adsorption, T
is the absolute temperature in K, R is the gas constant (8.314 J/
mol. K.). The relevant experimental data were used to calcu-
late the values of DG° (J/mol) at different temperatures (Eqs.
(7) and (8)), while DSo (J/mol) and DH° (KJ/mol) values were
evaluated using Eq. (9) from the slope and intercept of the plot
lnKC against 1/T (Fig. 13). The estimated thermodynamic
parameters were presented in Table 3. The negative values of
DG° at different temperatures indicate that the nature of
biosorption of the M.O dye process was spontaneous and
the negative value of DH° value detects that the process was
exothermic. Moreover, the positive value ofDS° indicated the
randomness increases at the interface of the aqueous solution
– adsorbent through the biosorption [44].
4. Conclusions
This study presented a potential technique for bioremediation
of non-biodegradable organic compounds (dyes) from wastew-
ater. The prepared biosorbent proved highly effective for the
adsorptive removal of M.O dye from aqueous solution in a
batch system. The results demonstrated that the maximum
removal efficiency of 96.52 % was obtained at optimum condi-
tions of pH 6.5, 50 mg/l M.O concentration, 1.5 g/l biosorbent
Biosorption of dye by immobilized yeast cells on the surface of magnetic nanoparticles
dosage, 110 rpm shaker, and 35 °C temperature. The immobi-
lized yeast cells on the surface of Fe3O4 MNPs contributed to
an increase in the surface area resulting in enhanced biosorp-
tion and increased removal efficiency. Therefore, the immobi-
lization technique of biomass on the surface of Fe3O4 MNPs is
a promising technique for preparing nanobiocatalyst with
great potential for bioremediation of industrial effluents. The
equilibrium data indicated that the biosorption was consistent
with the Freundlich isothermal model. Moreover, the results of
estimating the values of thermodynamic parameters of the
biosorption process indicated that the biosorption mechanism
of M.O was exothermic and spontaneous.
Declaration of Competing Interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgments
The authors acknowledge the support and encouragement
given by University of Technology, Department of Petroleum
Technology.
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